Conversion of solid fuels and products derived therefrom or other materials into valuable liquids



C. CONVERSION OF' SOLID FUELS AND PRODUCTS DERIVED THEREFROM April 18,1933. KRAucH Er AL 1,904,475

OR OTHER MATERIALS INTO VALUABLE LIQUIDS Original Filed Feb. 6. 1926 2Sheets-Sheet l Aplll 18, 1933. C KRAUCH |A| 1,904,476

CONVERSION OF SOLID FUELS AND PRODUCTS DERIVED THEREFROM OR OTHERMATERIALS INTO VALUABLE LIQUIDS Original Filed Feb. 6. 1926 2Sheets-Sheet 2 l g i 'a s i a Qs 'l "Y, MN W y fuel including coalPatented Apr. 18, 1933 i i UNirED STATES PATENT OFFICE CARL KRAUCH, OFLUDWIGSHAFEN-ON-THE-RHINE, AND MATELAS PIER, HEIDEL- BERG, GERMANY,ASSIGNORS, BY MESNE ASSIGNMENTS, TO STANDARD-I. G. COM- PANY, OF LINDEN,NEW JERSEY, A CORPORATION 0F DELAWARE CONVERSION 0F SOLID FUELS A NDPRODUCTS DERIVED 'IHIElRIlFROlVIv 0R OTHER MATERIALS INTO VALUAIBLELIQUIDS Original application led.

February 6, 1926, Serial No. 86,646, and in Germany November 7, 1925.Divided and this application led April 7, 1927. Serial No. 181,887.

One of the most important and widely agitated problems in the industrialworld has for a. long time been how to produce good gasoline or othervaluable liquid fuels from solid in all its varieties and wood, andproducts of distillation 'or mineral oils especially heavy oils.

One attempt at the solution of this problem has been made by theso-called liquefaction of coals by means of hydrogen or by destructivehydrogenation of tars or oils under high pressure at high temperaturebut this has not reached application industrially because of anunsatisfactory speed and rate of the conversion.

By the process described in the specification of the originalapplication No. 86,646 file d February 6th, 1926, of which this is adivision, we claim to have successfully solved this problem for thefirst time and to beable to produce good pure liquid fuels, includingalso benzines from solid fuels and to convert also tars obtained fromsolid fuels and also heavy mineral oils, or crude oils, or residues intomore valuable liquid products, including benzines, by a processeconomical in material, time, labour and wear of the apparatus.

In arriving at this result we have made several discoveries orinventions to certain of which this application is directed.

We conceived the idea of applying a catalyst to said solid fuel or othermaterials, in connection with said hydrogenizing high pressure and hightemperature process, but found that an improvement of the process couldnot be obtained at all or at least not in a continued operation.

Thereafter we discovered that the cause of this drawback was the sulfurpresent in the treated material, and by experimenting discovered certaincatalysts which would work satisfactorily under the existing conditionsnotwithstanding the presence of the sulfur or sulfur compounds.

Thereupon we found that the apparatus were attacked too rapidly forindustrial success due to several influences, chiefly to the presence ofsulfur mostly found in the initial materials, and that many troubles inthe operations and also other drawbacks were hereby caused, and wediscovered that under the conditions existing in the process ofhydrogenizing, whether with an addition of the aforementioned or othercatalysts or in the absence of catalysts an apparatus composed of orlined with aluminium would behave excellently. Even with materials richin sulfur, for example Mexican Panuca oil, metallic aluminium as such orin the form of its alloys is not attacked by the contact with hotgaseous, liquid or solid material, and when using it as a lining it maybe used until near its melting point.

As examples of aluminium alloys suitable for the construction ofapparatus in accordance with the present invention may be nientioned analloy consisting of 4 per cent of f copper, 0.5 per cent of manganese,0.5 per cent of magnesium and the remainder of aluminium or an alloyconsisting of 1.5 per cent of silicon, 0.8 per cent of magnesium, 0.4per centof iron and the remainder of aluminium or an alloy consisting of0.5 per cent of silicon, 3 per' cent of copper, 0.6 per cent ofmanganese, 0.1 per cent of lithium, 0.4 per cent ofjiron, 12 per cent ofzinc and the remainder of aluminium or an alloy consisting of 2.5 percent of manganese, 2.2 per cent of magnesium, 0.2 per cent of antimonyand the remainder of aluminium or an alloy consisting of 8 per cent ofcopper and the remainder of aluminium, or an alloy consisting of 13 percent of silicon and the remainder of aluminium.

As regards the materials to be treated, the invention can be applied toany sort of solid fuels, for example, hard or soft coal, brown coal,lignite, peat, wood, or similar materials, mineral oils, shale oils, orother solid or liquidbitumina, also distillation or extraction productsof all of them, such as tars obtained from them, whether by ordinarydestructive distillation or by low temperature carbonization, or browncoal bitumen, or tars or oils obtained by pressure hydrogenation ofsolid or liquid fuels, or components or conversion products of all abovementioned materials, such as cracked products, coumarone or any otherresins or residues of their distillation, pitch, asphaltum and so on, ormixtures of several such products with each other, also of solids withliquids or of one or more of such products with other suitable organicliquids. y

The preferred form of carrying out the process is generally a continuousoperation with a stream of the gases and with an excessthereof over therequired quantity and preferably while maintaining the desired pressureby adding fresh gas and passing the gas either by circulation throughone or more reaction vessels or through a succession of several reactionVessels. The material to be converted is supplied at a proper place andthe products are separated from the reaction gases by cooling.

The gases serving for the reaction may consist of hydrogen alone or ofmixtures containing hydrogen, for example a mixture of hydrogen withnitrogen, or Water gas, or hydrogen mixed with carbon dioxid, hydrogensulfide, Water vapor or methane or other hydrocarbons. Or the hydrogenmay be generated in the reaction chamber by the interaction of Water andcoal, carbon monoxid, hydrocarbons and the like.

The process is best carried out under elev vated or even stronglyelevated pressure andl most suitably With a stream of the gas passedthrough or over the material to be treated or carrying it along throughthe reaction vessel by which method the production obtained by theprocess is very large.

Depending on the conditions o-f Working,

for example temperature and pressure em-v ployed or duration of thetreatment, the products are poor or rich in products of low boilingpoint. Generally the temperature ranges between 300 and 700 C., and whenWorking under pressure, it should amount to 20, 50 or more atmospheres.

Compounds obtained by the aforedesc'ribed hydrogenation treatment ofsolid fuels, tars, mineral oils and other materials referred to, whichcompounds may be `comprised by the term destructively hydrogenized fuelsare generally very low in sulfur or even completely free therefrom andare excellently suitable for use as fuel for internal combustionengines.

In the accompanying drawings, an apparatus for carrying out the onestage process and an apparatus for carrying out the two stage process,both being continuous, are illustrated diagrammatically, partly invertical section. Our invention is not limited to the apparatusillust-rated therein. hoW-' ever, but may be varied at will inaccordance with the conditions of working.

Referring to the drawing in Fig. 1 in detail, reference numeral 1indicates a feed line from any convenient source of liquid raw material.The line 1 discharges to a grinding mechanism 2 fitted with ahopper 3through which solid materials may be admitted. If desired, the grindingmechanism can be by-passed by line 1a when no solid materials are used.The suspension of solid material in liquid or the liquid alone may bethen forced by pump 5 through a line 4 to a heat exchanger 6 and thenceby line 7 into a reaction chamber 8. The reaction chamber is constructedin any preferred manner and should be adapted to withstand highpressures, for example above 20-100 or even as high as 800 atmospheres,as Well as the corrosive effects of the reactants. The vessel ispreferably protected from loss of heat by a suitable insulating cover 9and may be heated by electric coils 10 which are arranged Within thedrum. The contents of the drum are preferably kept in a state ofagitation by meansof a stirring mechanism 11 and, if desired, suitablecatalytic materials 11 as indicated above may be attached to thestirring mechanism so that the catalyst is brought into intimate contactwith the contents of the vessel.

Hydrogen under high pressure is forced through a line 12, heat exchanger13 and then by line 14 into the base of the reactor 8 into which it ispreferably discharged through a spray pipe 15. A liquid level may bemaintained in the drum, for example at the point 16a and gas andvaporous products may be continuously Withdrawn by vapor line 16 whichis in communication with exchanger 13 and a cooling coil or condenser17. The condensate and gas is discharged into a separation drum 18 fromwhich the distillate is removed by line 19 to storage, not shown. Thegas may be taken off by a pipe 20 to a purifying system indicated at 21,and which may comprise a scrubbing system preferably carried out at highpressure using, for example, soda to remove hydrogen sulphide and oil toremove hydrocarbon constituents from gas. Purified gas is thenrcompressed by a booster pump 22 and is forced again into the hydrogenfeed line 12. Fresh hydrogen may be introduced by line 23. If desired,oil may be continuously removed from the drum by a line 24 whichcommunicates with heat exchanger 6 and which is Withdrawn to storage,not shown, by asuitable line 25.

Referring now to the drawing in Fig. 2 a suitable system is shown forconverting solid materials into light liquid oils by two steps. Wherepossible, the same numeral has been used in Fig. 2 as has already beenindicated in Fig. 1. Hydrocarbon oil is withdrawn from any suitablestorage, not shown. by a line 1 and may be forced through a grindingmechanism 2 which is fitted with the hopper 3 for the introduction ofsolid material, vsuch as coal, lignite or the like. The pump 5 forcesthis mixture through line 4 into the first oven indicated by the numeral8a. This.` oven may be constructed in the 'zol same manner as the oven 8shown in Fig. l and similar parts are designated by the same numerals. Aheavy liquefied material is withdrawn from the base of the oven 8a andmay be continuously discharged into the second oven indicated by 8b.This oven may be packed with a suitable solid catalytic materialindicated at 11 and with the exception that no stirring mechanism isused it may be constructed similarly to oven 8a.

Hydrogen is forced under high pressure from the line 12, as before,through a heat exchanger 13 and by line 14 and branches 14a and 146 intooven 8a and 8b respectively. Vaporous products and gas are removed fromboth ovens by vapor line 16a and 1Gb respectively which may dischargethrough a single exchanger 13 to condenser 17. The light oils areseparated from the gases in the separator 18 from Which the oil isremoved by 19 and the gases may be removed, purified and recompresscd asindicated in Fig. 1. Heavy oil may be continuously Withdrawn from theoven 8b and a part or the whole thereof may be continuously dischargedthrough a line 24a, cooler 26 and conducted by line 25 to any suitablestorage. If desired, a part of this oil may be recirculated to line 1 orto line 4 by means of recirculation line 24?), pump 27 and either of thetwo lines 28 or 29, as vis desired.

In the operation of this system solid carbonaceous material containingash may be to the first oven and a suficient quantity of the oilcontaining inorganic material may be led from the system by the lines24a and 25 so as to prevent accumulation within the system. Freshhydrocontinuously fed carbon oil may be continuously fed in suf-Y[icient quantity to carry in the solid material or if desired, a part ofthe oil withdrawn from the second oven, either containing ash or fromwhich the ash has been removed by filtration, settling centrifugal meansor the like may be recirculated for the purpose of bringing in the freshsolid material.

In the following example the time of reaction varies considerably, asmight be supposed, depending on the nature of the raw material, theactivity of the catalyst, temperature, pressure and the like. Inpractice it is desirable to make a few preliminary runs in order todetermine the time required for the best yields under a given lset ofconditions. Generally speaking, with batch operations the total time maybe from two to ten hours or more, depending on the yield desired, whilewith continuous operations the time is usually shorter. Whencontinuously feeding liquid or diiicultly vaporizable oils, the rate ofow may be in the neighborhood of .3 to .8 volumes of oil per hour pervolume of the reaction space. Vaporous materials may be treated athigher temperatures and the feed rate may consequently be one or evenone and one-half volumes per hour per volume of reaction space. Thevolume of hydrogen may likewise vary considerably and should always,.ofcourse, be in excess of that actually required for the conversion; forexample, the rate of ioW of hydrogen may be in excess of about 600litrles per kilogram of carbonaceous materia f f All parts of theapparatus liable to .assume a temperature above 300o C. are lined withaluminium.

The following example will serve to further explain how our invention iscarried out in practice, but we do not restrict our invention to thisexample.

E :sample Dark-colored residues of an American rock oil which atordinary temperature are nearly solid and have a strongly unsaturatedcharacter are incorporated with an excess of a gas mixture composed ofthree parts, by volume, of hydrogen and 1 part of nitrogen andcontinuously passed under a pressure of 200 atmospheres and atemperature of from 450 degrees to 500 degrees centigrade over a contactmass prepared from an intimate mixture of 70 parts, by weight, ofammonium molybdate and 30 parts of aluminium hydroxid. The reactionvessel containing the said catalytic mass is lined with aluminium as areall other parts of the apparatus liable to assume a high temperature,say of more than 300 degrees centigrade, which lining prevents both adecomposition of the hydrocarbons with a deposition of coke or soot anda destruction of the apparatus by the action of the sulfur compoundscontained in the rock oil residues. A nearly colorless, thin andsaturated product is obtainedbesides a little methane, consisting ofpercent of colorless petrol boiling up to 150 degrees and 10 percent ofa mobile, yellowish product of a higher boiling point.

lVhat we claim is:

1. The process of converting carbonaceous substances, such as solid andliquid fuels, distillation and extraction products thereof, intovaluable liquids, which comprises subjecting such substances todestructive hydrogenation by means of an added hydrogenating gas andheat at a temperature of between about 300 and 500 C. and at a pressureof at least 20 atmospheres in a reaction vessel, the inner surface ofwhich consists of an alloy of aluminium solid under the conditions ofworking.

2. The process of converting carbonaceous substances, such as solid andliquid fuels, distillation and extraction products thereof, intovaluable liquids, which comprises subjecting such substances todestructive hydrogenation by means of an added hydrogenating gas and theat at a temperature of between about 300 and 500 C. and at a pressureof at least 20 atmospheres in a reaction vessel, theinner surface ofwhich consists of aluminium.

3. The process of converting carbonaceous substances such as solid andliquid fuels, distillation and extraction products thereof into Valuableliquids, which comprises subjecting such substances to destructivehydrogenation by means of a hydrogenating gas and heat at a temperatureof between about 300 and 500 C. in the presence of a catalyst immune tosulphur poisoning and at a pressure of at least 20 atmospheres andentirely confining the reacting materials by means of surfacesconsisting of aluminium.

4'. The process of converting carbonaceous substances such as solid andliquid fuels, distillation and extraction products thereof into valuableliquids, which comprises subjecting such substances to destructivehydrogenation by means of a hydrogenating gas and heat at a temperatureof between about 300 and 500 C. in the presence of a catalyst immune tosulphur poisoning and at a pressure of at least l20 atmospheres andentirely confining the reacting,- materials by means of surfacesconsisting of an alloy of aluminium solid under the conditions ofWorking.

In testimony whereof We have hereunto set our hands.

CARL KRAUCH. MATHIAS PIER.

